KR20070014507A - Manufacturing method of electrodes for zn/air fuel cell - Google Patents
Manufacturing method of electrodes for zn/air fuel cell Download PDFInfo
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- KR20070014507A KR20070014507A KR1020050069194A KR20050069194A KR20070014507A KR 20070014507 A KR20070014507 A KR 20070014507A KR 1020050069194 A KR1020050069194 A KR 1020050069194A KR 20050069194 A KR20050069194 A KR 20050069194A KR 20070014507 A KR20070014507 A KR 20070014507A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Description
도 1은 본 발명의 일 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법의 공정을 개략적으로 보여주는 도면.1 is a view schematically showing a process of a method of manufacturing an electrode for a Zn / Air fuel cell according to an embodiment of the present invention.
도 2는 본 발명의 다른 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법의 공정을 개략적으로 보여주는 도면.2 is a view schematically showing a process of a method of manufacturing an electrode for a Zn / Air fuel cell according to another embodiment of the present invention.
도 3은 본 발명에 따른 Zn/Air 연료전지용 전극의 제조방법에 의해 제조된 전극의 전기화학적 특성을 보여주는 도면.Figure 3 is a view showing the electrochemical characteristics of the electrode produced by the method for producing an electrode for Zn / Air fuel cell according to the present invention.
본 발명은 아연/공기(Zn/Air) 연료전지용 전극의 제조방법에 관한 것으로서, 특히 전극물질이 액상의 슬러리 상태가 아닌 분말 상태에서 전극의 제조가 가능하며, 또한 일정 유압 하에서 집전체와 전극 물질을 펠릿 몰드로 일체화시켜 제조할 수 있는 아연/공기(Zn/Air) 연료전지용 전극의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing an electrode for a zinc / air fuel cell, and in particular, the electrode material can be manufactured in a powder state instead of a liquid slurry state, and the current collector and electrode material under constant hydraulic pressure. The present invention relates to a method for manufacturing a zinc / air (Zn / Air) fuel cell electrode which can be manufactured by integrating a pellet into a mold.
Zn/Air 연료전지는 소형, 경량화에 대한 욕구를 충족시킬 수 있는 차세대 전지로서 공기극과 반응성이 있는 애노드(anode)와 무한대로 존재하는 캐소드 (cathode) 반응물질과의 전기화학적 결합은 매우 높은 체적당 에너지 밀도와 중량당 에너지 밀도를 제공한다. 이것은 리튬 2차 고분자 전지에 비해서 고에너지밀도(이론값≒1,090Wh/kg)를 가지고 있으며, 또한 저가로 제조할 수 있는 장점을 가지고 있다. Zn / Air fuel cell is the next generation battery that can satisfy the need for small size and light weight. The electrochemical combination of anode which is reactive with air electrode and cathode reactant which is infinity is very high volumetric. Energy density and energy density per weight. It has a high energy density (theoretical value # 1,090 Wh / kg) compared to lithium secondary polymer battery, and also has the advantage that it can be manufactured at low cost.
특히, Zn/Air 연료전지는 방전전압이 균일하고, 보존특성이 좋으며, 오염물질이 없는 환경친화성이라는 장점이 있다. 이러한 큰 장점에도 불구하고 Zn/Air 연료전지의 용도는 1회 사용하고 버리는 1차 전지의 용도로 주로 보청기 등에 이용되어 왔다. In particular, Zn / Air fuel cells have the advantages of uniform discharge voltage, good storage characteristics, and environmental friendliness without contaminants. Despite these great advantages, Zn / Air fuel cells have been used primarily in hearing aids for primary batteries that are used once and discarded.
이는 Zn/Air 연료전지가 가지는 단점, 즉, 전해질이 외부의 수증기압에 따른 영향으로 발생하는 전지의 성능저하, 제한된 출력특성, 음극의 부식에 의한 수소 발생, 무엇보다 충/방전에 따른 음극의 덴드라이트(dendrite), 충전 중 촉매전극과 지지전극의 산화반응 등 해결해야 할 많은 문제점이 있기 때문이다. This is a disadvantage of Zn / Air fuel cells, that is, the performance degradation of the battery caused by the influence of the external water vapor pressure, the limited output characteristics of the battery, the hydrogen generated by the corrosion of the negative electrode, and most of all, This is because there are many problems to be solved, such as a dry load, an oxidation reaction between the catalyst electrode and the support electrode during charging.
그러나, 지난 30년간 꾸준한 노력으로 많은 문제점들이 해결되었거나 해결방안이 제시되어 기술적으로 기존의 2차 전지를 대체할 수 있는 차세대 전지로서 부각되고 있는 중이다.However, many problems have been solved or solutions have been suggested by the steady efforts over the past 30 years, and are emerging as next-generation batteries that can replace conventional secondary batteries.
Zn/Air 연료전지용 전극을 제조하기 위한 종래의 기술은 슬러리 상태의 전극 물질을 집전체에 페이스팅(pasting)하는 방법을 이용하여 왔다. 이 방법은 전극물질이 액상의 슬러리 상태이어야만 제조 가능한 방법으로서 리튬전지 등의 일반적인 전극 제조에 널리 응용되고 있는 전극 제조방법이다.Conventional techniques for manufacturing electrodes for Zn / Air fuel cells have used a method of pasting a slurry electrode material to a current collector. This method is a method that can be produced only when the electrode material in the liquid slurry state is an electrode manufacturing method widely applied to the production of general electrodes such as lithium batteries.
본 발명은 이상과 같은 사항을 감안하여 창출된 것으로서, 전극물질이 액상의 슬러리 상태가 아닌 분말 상태에서 전극의 제조가 가능하며, 동시에 일정 유압 하에서 집전체와 전극 물질을 펠릿 몰드로 일체화시켜 제조할 수 있는 Zn/Air 연료전지용 전극의 제조방법을 제공함에 그 목적이 있다.The present invention has been made in view of the above matters, and the electrode material can be manufactured in a powder state instead of a liquid slurry state, and at the same time, the collector and the electrode material can be manufactured by integrating the current collector and the electrode material into a pellet mold under a certain hydraulic pressure. It is an object of the present invention to provide a method for manufacturing an electrode for a Zn / Air fuel cell.
상기의 목적을 달성하기 위하여 본 발명의 일 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법은,In order to achieve the above object, a method of manufacturing an electrode for a Zn / Air fuel cell according to an embodiment of the present invention,
a) 전극 물질의 출발원료로서 분말 상태의 Zn 또는 ZnO를 준비하는 단계;a) preparing Zn or ZnO in powder state as starting material of the electrode material;
b) 상기 분말상태의 전극 물질을 집전체와 함께 펠릿(pallet) 몰드 압착기에 넣은 후, 상호 압착하는 단계; 및b) placing the powdered electrode material together with a current collector in a pellet mold press, followed by mutual compression; And
c) 상기 펠릿 몰드 압착기에 유압기로 일정 압력을 가하여 최종적으로 전극 물질과 집전체가 일체화된 펠릿 몰드의 Zn/Air 연료전지용 전극을 제조하는 단계를 포함하여 구성된 점에 그 특징이 있다.and c) applying a predetermined pressure to the pellet mold compactor to finally produce a Zn / Air fuel cell electrode of the pellet mold in which the electrode material and the current collector are integrated.
또한, 상기의 목적을 달성하기 위하여 본 발명의 다른 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법은,In addition, in order to achieve the above object, a method of manufacturing an electrode for a Zn / Air fuel cell according to another embodiment of the present invention,
a) 전극 물질의 출발원료로서 Zn 또는 ZnO를 모재로 하여 기능성 첨가제 및 접합제를 포함한 복합원료를 일정 화학량론에 의거하여 혼합하는 단계; a) mixing a composite material including a functional additive and a binder based on a certain stoichiometry, based on Zn or ZnO as a starting material of the electrode material;
b) 용기에 상기 혼합물과 증류수를 소정의 부피비로 넣은 다음 소정 시간 동안 유지하며 교반하는 단계; b) putting the mixture and distilled water in a predetermined volume ratio in a container, and then holding and stirring for a predetermined time;
c) 상기 교반된 혼합물에 열을 가하여 수분을 증발시키는 단계; c) heating the stirred mixture to evaporate moisture;
d) 상기 수분 증발 단계 후 얻어진 고체화합물을 분쇄과정을 통해 분말 상태로 Zn/Air 연료전지용 전극 물질을 생성하는 단계; d) generating an electrode material for a Zn / Air fuel cell in a powder state by grinding the solid compound obtained after the water evaporation step;
e) 상기 분말 상태의 전극 물질을 펠릿 몰드 압착기에 집전체와 함께 넣어 상호 압착하는 단계; 및e) compressing the electrode material in the powder state together with a current collector in a pellet mold press; And
f) 상기 펠릿 몰드 압착기에 의한 압착 공정 후 유압기로 펠릿 몰드 압착기에 압력을 가하여 최종적으로 전극 물질과 집전체가 일체화된 펠릿 몰드의 Zn/Air 연료전지용 전극을 제조하는 단계를 포함하여 구성된 점에 그 특징이 있다.f) pressurizing the pellet mold compactor with a hydraulic press after the compacting process by the pellet mold compactor to finally prepare a Zn / Air fuel cell electrode of the pellet mold in which the electrode material and the current collector are integrated. There is a characteristic.
여기서, 상기 단계 b)에서, 증류수를 소정의 부피비로 넣은 다음 적어도 5시간 내지 24시간 동안 유지시킨다.Here, in step b), distilled water is added at a predetermined volume ratio and maintained for at least 5 hours to 24 hours.
또한, 상기 단계 f)에서, 유압기로 펠릿 몰드 압착기에 적어도 5 ton 이상의 압력을 수초에서 2분 이내 동안 가한다.Further, in step f), a pressure is applied to the pellet mold compactor with a hydraulic press for at least 5 ton or more in a few seconds to within 2 minutes.
이하 첨부된 도면을 참조하면서 본 발명의 실시예를 상세히 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 일 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법의 공정을 개략적으로 보여주는 도면이다.1 is a view schematically showing a process of a method of manufacturing an electrode for a Zn / Air fuel cell according to an embodiment of the present invention.
도 1을 참조하면, 본 발명의 일 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법에 따라 먼저 전극 물질의 출발원료로서 분말 상태의 Zn 또는 ZnO를 준비한다(단계 S101). Referring to FIG. 1, according to a method of manufacturing an electrode for a Zn / Air fuel cell according to an embodiment of the present invention, first, a powder Zn or ZnO is prepared as a starting material of an electrode material (step S101).
그런 후, 상기 분말상태의 전극 물질을 집전체와 함께 펠릿 몰드 압착기에 넣은 후, 상호 압착한다(단계 S102). Then, the powdered electrode material is put into a pellet mold presser together with the current collector, and then pressed together (step S102).
그런 다음, 상기 전극 분말과 집전체가 상호 압착된 상태로 있는 펠릿 몰드 압착기에 유압기로 일정 압력을 가하여 최종적으로 전극 물질과 집전체가 일체화된 펠릿 몰드의 Zn/Air 연료전지용 전극을 제조한다(단계 S103).Then, a pressure is applied to a pellet mold presser in which the electrode powder and the current collector are pressed together to produce a Zn / Air fuel cell electrode of a pellet mold in which the electrode material and the current collector are finally integrated (step). S103).
도 2는 본 발명의 다른 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법의 공정을 개략적으로 보여주는 도면이다.2 is a view schematically showing a process of a method of manufacturing an electrode for a Zn / Air fuel cell according to another embodiment of the present invention.
도 2를 참조하면, 본 발명의 다른 실시예에 따른 Zn/Air 연료전지용 전극의 제조방법에 따라 먼저 전극 물질의 출발원료로서 Zn 또는 ZnO를 모재(M1'출발원료)로 하여 기능성 첨가제(M2'출발원료) 및 접합제(M3'출발원료)를 포함한 복합원료를 일정 화학량론에 의거하여 혼합한다(단계 S201). 여기서, 상기 기능성 첨가제는 수소발생반응 및 부식의 억제제를 원료로 포함할 수 있으며 이들 혼합물의 결합을 위해 접합제가 동시에 사용될 수 있다. Referring to FIG. 2, according to a method of manufacturing an electrode for a Zn / Air fuel cell according to another embodiment of the present invention, first, a functional additive (M2 ') is obtained by using Zn or ZnO as a base material (M1 ′ starting material) as a starting material of an electrode material. A starting material) and a binder (M3 'starting material) are mixed based on a certain stoichiometry (step S201). Here, the functional additive may include a hydrogen generating reaction and an inhibitor of corrosion as a raw material and the binder may be used simultaneously for the combination of these mixtures.
이렇게 하여 출발원료의 혼합이 완료되면, 용기에 상기 혼합물과 증류수를 소정의 부피비로 넣은 다음 소정 시간 동안 유지하며 교반한다(단계 S202). 이때, 증류수를 소정의 부피비(예컨대, 혼합물:증류수=1:3)로 넣은 다음, 혼합물과 증류수가 충분한 혼합과 교반이 이루어지도록 적어도 5시간∼24시간 동안 유지시킨다. In this way, when the mixing of the starting materials is completed, the mixture and distilled water are put in a container at a predetermined volume ratio and then maintained for a predetermined time and stirred (step S202). At this time, distilled water is added at a predetermined volume ratio (eg, mixture: distilled water = 1: 3), and then maintained for at least 5 to 24 hours to allow sufficient mixing and stirring of the mixture and distilled water.
이렇게 하여 혼합물과 증류수가 충분히 교반되었으면, 그 교반된 혼합물에 열을 가하여 수분을 증발시킨다(단계 S203).When the mixture and the distilled water are sufficiently stirred in this way, heat is added to the stirred mixture to evaporate the water (step S203).
그리고, 수분 증발 단계 후 얻어진 고체화합물을 분쇄과정을 통해 분말 상태로 Zn/Air 연료전지용 전극 물질을 생성한다(단계 S204).Then, the solid compound obtained after the water evaporation step to produce a Zn / Air fuel cell electrode material in a powder state through the grinding process (step S204).
그런 후, 상기 분말 상태의 전극 물질을 펠릿 몰드 압착기에 집전체와 함께 넣은 후 상호 압착한다(단계 S205). Then, the powdered electrode material is put together with the current collector in the pellet mold presser and then pressed together (step S205).
이렇게 하여 펠릿 몰드 압착기에 의한 압착 공정이 완료된 후, 유압기로 펠릿 몰드 압착기에 압력을 가하여 최종적으로 전극 물질과 집전체가 일체화된 펠릿 몰드의 Zn/Air 연료전지용 전극을 제조한다(단계 S206). 여기서, 유압기로 펠릿 몰드 압착기에 적어도 5 ton 이상의 압력을 수초에서 2분 이내 동안 가한다.In this manner, after the pressing process by the pellet mold presser is completed, pressure is applied to the pellet mold presser with a hydraulic press to finally prepare a Zn / Air fuel cell electrode of the pellet mold in which the electrode material and the current collector are integrated (step S206). Here, a pressure is applied to the pellet mold press with a hydraulic press for at least 5 ton or more in a few seconds to within 2 minutes.
한편, 도 3은 본 발명에 따른 Zn/Air 연료전지용 전극의 제조방법에 의해 제조된 전극의 전기화학적 특성을 보여주는 도면으로서, 본 발명의 제조방법에 의해 얻어진 전극이 전지시스템에서 전기화학적으로 실제로 효용성을 가짐을 입증하고 있다. 본 발명의 제조방법에 의해 제조된 전극의 전기화학적 특성을 알아보기 위하여 백금(Pt)을 상대(counter) 전극, 그리고 Hg/HgO를 기준(reference) 전극으로 하여 1 mV/s의 스캐닝(scanning) 율(rate)로 싸이클릭 볼타모그램(cyclic voltammogram)을 실시하였다.On the other hand, Figure 3 is a view showing the electrochemical characteristics of the electrode produced by the method of manufacturing the electrode for Zn / Air fuel cell according to the present invention, the electrode obtained by the manufacturing method of the present invention is actually electrochemically useful in the battery system Prove that you have Scanning of 1 mV / s using platinum (Pt) as a counter electrode and Hg / HgO as a reference electrode to investigate the electrochemical characteristics of the electrode manufactured by the manufacturing method of the present invention Cyclic voltammogram was performed at the rate.
이상의 설명에서와 같이, 본 발명에 따른 Zn/Air 연료전지용 전극의 제조방법은 액상의 슬러리 상태가 아닌 분말 상태만으로도 전극 제조가 가능하다. 또한, 일정 유압 하에서 집전체와 전극 물질을 펠릿 몰드로 일체화시켜 제조할 수 있는 장점이 있다. As described above, the method for manufacturing an electrode for a Zn / Air fuel cell according to the present invention can be produced electrode only in a powder state, not a liquid slurry state. In addition, there is an advantage that can be manufactured by integrating the current collector and the electrode material into a pellet mold under a certain hydraulic pressure.
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